CN108531746B - Extracting agent for separating noble metal and method for extracting and separating noble metal by using extracting agent - Google Patents

Extracting agent for separating noble metal and method for extracting and separating noble metal by using extracting agent Download PDF

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CN108531746B
CN108531746B CN201710121623.8A CN201710121623A CN108531746B CN 108531746 B CN108531746 B CN 108531746B CN 201710121623 A CN201710121623 A CN 201710121623A CN 108531746 B CN108531746 B CN 108531746B
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gold
platinum
hydrochloric acid
palladium
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CN108531746A (en
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赵志钢
杨帆
陈鹏
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Zhongkexin Lanthanide Xiamen Technology Co ltd
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Xiamen Institute of Rare Earth Materials
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B11/06—Chloridising
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
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    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/34—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing sulfur, e.g. sulfonium
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Abstract

The invention discloses an extracting agent for extraction and separation and an extraction and separation method applying the extracting agent, wherein in the extracting agent, the loading rate of the extracting agent in an organic solvent is improved according to different alkyl chain selections; and increase its hydrophobicity; due to the stability of the chemical structure, the reutilization of the extracting agent is correspondingly improved, and the environmental protection is realized; by controlling the hydrochloric acid concentration, separation between gold and other precious metals and/or other metals, platinum, palladium, rhodium and other precious metals can be achieved. The extraction separation method has the following advantages: (1) synthesizing a novel extracting agent by a simple method; (2) extracting and separating gold by using a solution extraction mode; (3) the back extraction of gold and other metals and/or other noble metals is realized by using a back extractant such as thiourea; (4) the repeatability experiment proves that the process method is simple, environment-friendly and convenient to operate, and can realize actual industrial production.

Description

Extracting agent for separating noble metal and method for extracting and separating noble metal by using extracting agent
Technical Field
The invention belongs to the technical field of extraction, and relates to an extracting agent for separating noble metals, a preparation method of the extracting agent, and a method for extracting and separating noble metals by using the extracting agent.
Background
Noble metal (noble metal) is a strategic reserve material and mainly comprises 8 metal elements such as gold, silver and platinum group metals. It is often used as a valuable jewel case, currency, etc. because of its extremely stable physical, chemical properties, etc.; in addition, in modern science and technology, noble metals are mainly used in industrial and scientific research, including aerospace, marine, chemical, electronic, metallurgical, and the like. Due to the scarcity and wide application performance of precious metal resources, research and development of precious metal mining and secondary resource recovery technologies are urgently needed.
Gold (Au) is an important metal resource. From ancient times to present, they have been available as hard currency; in addition, gold has strong chemical stability, so that the gold is more and more widely applied, and plays an important role in the aspects of electronics, modern communication, aerospace, medicine and the like. However, gold deposits are scarce and there are about 13.74 million tons of gold deposits worldwide, so it is of considerable interest to develop a technology for secondary resource recovery of gold. Metallurgy is one of the important methods for extracting gold and generally includes electrometallurgy, hydrometallurgy and pyrometallurgy. The extraction and separation of gold is mainly applied to hydrometallurgy, and in the hydrometallurgy, solution extraction has the advantages of high speed, high selectivity, large extraction flux and the like and is widely applied, so that an extracting agent for gold extraction and separation is designed and developed, and the extraction and separation efficiency of gold in solution extraction can be improved.
At present, the defects that the selection of an extracting agent is limited, the extraction and separation efficiency of gold in a solution is not high and the like in the traditional hydrometallurgy process are overcome; the extraction and separation efficiency of gold in the solution extraction method is improved by improving the extracting agent, which has important research significance.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide an extracting agent for separating noble metals. The extractant of the present invention contains functional groups such as amide, ether/thioether, carboxylic acid/thiocarboxylic acid, etc., and has excellent characteristics for extraction and separation of noble metals, and the characteristics such as hydrophobicity, organic loading rate, etc. can be adjusted by the composition of the branched chain.
The invention also aims to provide a method for extracting and separating the noble metals (including the noble metals and other metals, particularly between gold and other (noble) metals) by using the extracting agent. The method comprises at least the following features: (1) the novel extractant is used, and has high-efficiency separation property on noble metals; in addition, the hydrophobicity of the branched chain can be adjusted through the composition of the branched chain, so that the extracting agent has higher repeated utilization rate and is more environment-friendly. (2) Research shows that the concentration of the hydrochloric acid aqueous solution in the aqueous phase is different, the separation characteristics of gold and other metals and/or other noble metals, platinum, palladium and rhodium and other noble metals and/or other metals are different, and therefore, the extraction separation coefficient can be remarkably improved by adjusting the concentration of the hydrochloric acid aqueous solution. (3) It is found that the organic solvents in the organic phase are different, and the separation characteristics of gold and other metals and/or other noble metals, platinum, palladium and rhodium and other noble metals and/or other metals are different, so that the extraction separation coefficient is remarkably improved by selecting different organic solvents. (4) Researches find that the separability of the extracting agent can be enlarged by regulating and controlling the extraction time, and the extraction separation coefficient is improved. (5) A new stripping agent is discovered and used in the invention, and the extraction separation coefficient is obviously improved.
The purpose of the invention is realized by the following technical scheme:
an extractant for separating noble metals, which has a structure shown in formula (I):
Figure BDA0001237236300000021
wherein, X1、X2Identical or different, independently of one another, from the group-O-or-S-; r1、R2Same or different, independently from each other selected from H, C1～30Linear or branched alkyl of (a); and R is1、R2Not simultaneously selected from H.
Preferably, said R is1、R2Same or different, independently from each other selected from H, C1～18Linear or branched alkyl of (a); and R is1、R2Not simultaneously selected from H.
Also preferably, R1、R2Identical or different, independently of one another, from H, n-octyl, n-hexyl, isohexyl, n-butyl, 2-ethylhexyl, isobutyl or isooctyl; and R is1、R2Not simultaneously selected from H.
Preferably, said X1、X2And the same is selected from-O-.
According to the invention, the purity of the extractant is greater than or equal to 90%.
According to the invention, the noble metal is selected from gold (Au), silver (Ag) and platinum group metals (Pt, Pd, Rh, Ru, Os and Ir), preferably Au, Pt, Pd and Rh, most preferably Au.
The invention also provides a noble metal extraction and separation method, wherein the extraction and separation method adopts the organic phase containing the extractant for extraction and separation.
According to the invention, the extraction separation method is suitable for the extraction separation between noble metals, between noble metals and other metals (such as Cu and the like in associated ores containing noble metal ores), especially between gold and other metals and/or noble metals, between platinum, palladium and rhodium and other noble metals and/or other metals.
According to the invention, the method comprises the following steps:
judgment 1) first, it is confirmed whether gold is contained in the system to be separated, and if gold is contained, the procedure is started from step a1) below; starting from the following judgment 2) if gold is not contained;
A1) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11An aqueous phase P comprising an aqueous hydrochloric acid solution of gold and other metals and/or other noble metalsM11And an aqueous phase P containing a stripping agentB11；
B1) Will PE11And PM11Mixing, shaking and separating to obtain organic phase P containing goldE12And an aqueous phase P of hydrochloric acid containing other metals and/or other noble metals not containing goldM12；
C1) To PE12Adding PB11Mixing, shaking, and separating to obtain water containing goldPhase PB12And an organic phase P 'containing an extractant'E11；
Judging 2) confirming whether platinum is contained in the system to be separated, and if platinum is contained, starting from the following step A2); if platinum is not contained, starting from the following judgment 3);
A2) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11An aqueous phase P containing platinum and an aqueous hydrochloric acid solution of another noble metal and/or another metal excluding gold and platinumM21Or directly using P separated in the step B1) aboveM12And an aqueous phase P containing a stripping agentB11；
B2) Will PE11And PM21Or PE11And PM12Mixing, shaking and separating to obtain an organic phase P containing platinumE22And an aqueous phase P containing an aqueous hydrochloric acid solution of a noble metal other than gold and platinum and/or of another metalM22；
C2) To P obtained in step B2)E22Adding PB11Mixing, shaking and separating to obtain water phase P containing platinumB22And an organic phase P' containing an extractant "E11；
Determining 3) whether palladium is contained in the system to be separated, and if palladium is contained, starting from step a3) below; if palladium is not contained, starting from the following judgment 4);
A3) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11An aqueous phase P comprising an aqueous hydrochloric acid solution of palladium and other noble metals and/or other metals, excluding gold, platinum and palladiumM31Or directly using P separated in the step B2) aboveM22And an aqueous phase P containing a stripping agentB11；
B3) Will PE11And PM31Or PE11And PM22Mixing, shaking and separating to obtain an organic phase P containing palladiumE32And an aqueous phase P containing an aqueous hydrochloric acid solution of a noble metal other than gold, platinum and palladium and/or of another metalM32；
C3) To P obtained in step B3)E32Adding PB11Mixing, shaking and separating to obtain water phase P containing palladiumB32And an organic phase P 'containing an extractant'E11；
Judging 4) confirming whether rhodium is contained in the system subjected to preliminary separation, and if rhodium is contained, starting from the following step A4); if the rhodium is not contained, ending;
A4) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11Aqueous phase P comprising an aqueous hydrochloric acid solution of rhodium and of other noble metals and/or other metals not including gold, platinum, palladium and rhodiumM41Or directly using P separated in the step B3) aboveM32And an aqueous phase P containing a stripping agentB11；
B4) Will PE11And PM41Or PE11And PM32Mixing, vibrating and separating to obtain an organic phase P containing rhodiumE42；
C4) To P obtained in step B4)E42Adding PB11Mixing, shaking and separating to obtain water phase P containing rhodiumB42And an organic phase P' containing an extractant "E11。
According to the invention, the organic phase P containing the extractant for separating noble metals represented by the formula (I)E11The molar mass concentration of the metal is 0.005-4 mol/L, and the aqueous phase P of the hydrochloric acid aqueous solution containing gold and other metals and/or other noble metals isM11Wherein the concentrations of gold and other metals and/or other noble metals are 1-100 ppm, the concentration of hydrochloric acid is 0.005-10 mol/L, and the water phase P containing platinum and other noble metals and/or other hydrochloric acid aqueous solutions excluding gold and platinumM21Wherein the concentrations of platinum and other noble metals and/or other metals excluding gold and platinum are 1-100 ppm, respectively, the concentration of hydrochloric acid is 0.5-10 mol/L, and the aqueous phase P of the hydrochloric acid aqueous solution containing palladium and other noble metals and/or other metals excluding gold, platinum and palladiumM31Wherein the concentrations of palladium and other noble metals and/or other metals excluding gold, platinum and palladium are 1 to 100ppm, respectively, the concentration of hydrochloric acid is 0.1 to 0.5 mol/L, and the aqueous hydrochloric acid solution containing rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodiumAqueous phase P ofM41Wherein the concentration of rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodium is 1-100 ppm, the concentration of hydrochloric acid is 0.005-0.1 mol/L, and the water phase P containing stripping agentB11Molar mass concentration of (3) 0.01 × 10-3～1mol/L。
Preferably, the organic phase P containing the extractant for separating noble metal represented by the formula (I)E11The molar mass concentration of the metal is 0.01-2 mol/L, and the aqueous phase P of the hydrochloric acid aqueous solution containing gold and other metals and/or other noble metals isM11Wherein the concentrations of gold and other metals and/or other noble metals are 5-30 ppm, the concentration of hydrochloric acid is 0.005-10 mol/L, and the water phase P containing platinum and other noble metals and/or other hydrochloric acid aqueous solutions excluding gold and platinumM21Wherein the concentrations of platinum and other noble metals and/or other metals excluding gold and platinum are 5-30 ppm, respectively, the concentration of hydrochloric acid is 0.5-10 mol/L, and the aqueous phase P of the hydrochloric acid aqueous solution containing palladium and other noble metals and/or other metals excluding gold, platinum and palladiumM31Wherein the concentrations of palladium and other noble metals and/or other metals excluding gold, platinum and palladium are 5 to 30ppm, respectively, the concentration of hydrochloric acid is 0.1 to 0.5 mol/L, and the aqueous phase P of the aqueous solution of hydrochloric acid containing rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodiumM41Wherein the concentration of rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodium is 5-30 ppm, the concentration of hydrochloric acid is 0.005-0.1 mol/L, and the aqueous phase P containing stripping agentB11Molar mass concentration of (3) 0.05 × 10-30.5 mol/L, preferably 0.1 × 10-3～0.1mol/L。
According to the invention, the organic solvent in the organic phase may be n-dodecane, kerosene; the hydrochloric acid aqueous solution containing gold and other metals and/or other noble metals can be prepared by soaking gold and other metals and/or other noble metals in hydrochloric acid, the other metals can be copper, and the other noble metals can be platinum, palladium, rhodium, ruthenium, osmium, iridium and silver; the hydrochloric acid aqueous solution containing platinum and other noble metals and/or other metals excluding gold and platinum may be prepared by acid pickling platinum with other metals and/or other noble metals excluding gold and platinum, such as copper, such as palladium, rhodium, ruthenium, osmium, iridium, silver; the hydrochloric acid aqueous solution containing palladium and other noble metals and/or other metals excluding gold, platinum and palladium may be prepared by pickling palladium with hydrochloric acid and other metals and/or other noble metals excluding gold, platinum and palladium, the other metals may be copper, and the other noble metals may be rhodium, ruthenium, osmium, iridium, silver; the hydrochloric acid aqueous solution containing rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodium can be prepared by acid pickling rhodium and other metals and/or other noble metals excluding gold, platinum, palladium and rhodium, the other metals can be copper, and the other noble metals can be ruthenium, osmium, iridium and silver; the stripping agent can be thiourea or hydrazine.
According to the invention, the oscillation time is 10 seconds to 20 hours, preferably 30 seconds to 12 hours; the extraction temperature is 10-50 ℃.
According to the invention, the volume ratio of the organic phase containing the extracting agent for separating the noble metal shown in the formula (I), the aqueous phase containing the hydrochloric acid aqueous solution of the metal and the aqueous phase containing the stripping agent is (0.5-1.5): 0.5-5; preferably (0.5-1.5): (1.5-2.5): 1.5-2.5).
The invention has the beneficial effects that:
1. the invention provides an extracting agent for extraction and separation, wherein in the extracting agent, the loading rate of the extracting agent in an organic solvent is improved according to different alkyl chain selections; the hydrophobicity is improved, and the recycling performance of the extracting agent is correspondingly improved due to the stability of the chemical structure, so that the environment is protected; by controlling the hydrochloric acid concentration, separation between gold and other noble metals and/or other metals, platinum, palladium, rhodium and other noble metals and/or other metals can be achieved. The method has great value in industry.
2. The invention also provides an extraction and separation method using the extractant, which is an effective extraction and separation method for precious metal exploitation and secondary resource recovery, and realizes the separation of precious metals by changing the concentrations of the organic solvent and hydrochloric acid, the stripping agent and the oscillation mode and controlling the extraction time.
3. The extracting agent and the extracting method have the following advantages: (1) synthesizing a novel extracting agent by a simple method; (2) extracting and separating gold by using a solution extraction mode; (3) the back extraction of gold and other metals and/or other noble metals is realized by using a back extractant such as thiourea; (4) the repeatability experiment proves that the process method is simple, environment-friendly and convenient to operate, and can realize actual industrial production.
The extracting agent takes metals commonly used in the current secondary resource recovery as interference elements, and in hydrochloric acid aqueous solution, the extracting agent utilizes the characteristic of high-efficiency separation of gold and other metals (platinum, palladium, rhodium, copper and the like) and develops the gold extracting and separating process based on the characteristic for separating and refining target metals. The gold is extracted and separated by utilizing the different separation characteristics of gold and other noble metals in hydrochloric acid aqueous solutions with different concentrations. The extraction separation performance of the extractant on gold in the aqueous solution and other metals and/or other noble metals is different under the condition of different hydrochloric acid concentrations and in different organic solvents; the separability of the extract can be enlarged by regulating and controlling time, and the extraction separation coefficient is improved.
Drawings
FIG. 1 is a flow diagram of a process for the extractive separation of noble metals according to a preferred embodiment of the present invention.
Detailed Description
As described above, the present invention provides an extractant for separating noble metals, which has a structure represented by formula (I):
Figure BDA0001237236300000071
wherein, X1、X2Identical or different, independently of one another, from the group-O-or-S-; r1、R2The same or different, and the same or different,are independently selected from H, C1～30Linear or branched alkyl of (a); and R is1、R2Not simultaneously selected from H.
In the invention, the preparation method of the extracting agent comprises the following steps:
a compound represented by the formula (II) and R1R2NH is used as a raw material, and the reaction is carried out at a certain temperature to prepare the extracting agent for separating the noble metal shown in the formula (I);
Figure BDA0001237236300000081
wherein, X1、X2、R1、R2Is as defined above.
In a preferred embodiment of the present invention, the preparation method specifically comprises the following steps:
1) respectively reacting a compound represented by the formula (II) with R1R2NH is dissolved in an organic solvent, wherein X1、X2、R1、R2Is as defined above;
2) and mixing the two solutions, and reacting to obtain the extracting agent for separating the noble metal shown in the formula (I).
Wherein the compound shown in the formula (II) is diglycolic anhydride.
Wherein, in the step 1), the organic solvent is selected from one or two of Dichloromethane (DCM) and acetone.
Wherein, in the step 2), the compound shown as the formula (II) and R1R2The molar charge ratio of NH is 0.5-1.5: 1.
In the step 2), the reaction temperature is 0-100 ℃, and preferably, the reaction temperature is 0-80 ℃.
In the step 2), the reaction time is 1-24 h, preferably 8-16 h, and further preferably 10-14 h.
Wherein, the purity of the extractant prepared in the step 2) is more than or equal to 90 percent.
During the reaction of step 2), the mixture gradually became clear, and when it was completely clear, the reaction was complete.
In a preferred embodiment of the present invention, the reaction further comprises: 3) washing the prepared extracting agent for separating the noble metal shown in the formula (I) by using high-purity deionized water to remove impurities, and then removing water and an organic solvent to obtain the extracting agent with higher purity.
Wherein, the step 3) of removing water is to add a water removing agent such as magnesium sulfate or sodium sulfate to the reaction product for removing water.
Wherein, the organic solvent removing process in the step 3) is to remove the organic solvent by performing rotary evaporation on the reaction product after water removal.
Wherein, the purity of the extractant prepared in the step 3) is more than or equal to 92 percent.
In a preferred embodiment of the present invention, the reaction may further comprise: 4) and 3) obtaining the extractant with higher purity by using acid washing or crystallization and other modes for the extractant treated in the step 3).
Wherein, the acid washing in the step 4) is to wash the reaction product by using 0.1M aqueous solution of sulfuric acid, hydrochloric acid, nitric acid and the like.
Wherein, the purity of the extractant prepared in the step 4) is more than or equal to 95 percent.
In one embodiment of the present invention, the preparation process of the extractant can be represented by the following chemical reaction process:
Figure BDA0001237236300000091
wherein R is1、R2Is as defined above.
In one embodiment of the present invention, the preparation process of the extractant can be represented by the following chemical reaction process:
Figure BDA0001237236300000092
wherein，R1、R2Is as defined above.
The extractant for extracting and separating the noble metal is only used for separating and purifying gold single metal, and can be applied to extracting and separating other metals.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it is to be understood that various changes or modifications may be made by one skilled in the art after reading the description herein, and equivalents may be applied thereto without departing from the scope of the invention defined by the claims.
Example 1
1.52g (13.1mmol) of diglycolic anhydride and 2.87g (11.9mmol) of R are weighed out1R2NH(R1Selected from isooctyl, R2Selected from isooctyl) respectively dissolved in a dichloromethane organic solvent of 20m L, the two solutions are mixed and reacted at 25 ℃, the mixed solution gradually becomes clear in the reaction process, and when the mixed solution is completely clear, the reaction is completed (about reaction 12h), and the extractant shown in the formula (I) is prepared (wherein, X is X)1And X2Is identically a-O-, R1And R2The same is isooctyl); washing the prepared extractant with high-purity deionized water to remove impurities, adding magnesium sulfate into the product after washing, filtering to obtain a product without water, removing the organic solvent from the treated product through a rotary evaporation condenser, and drying in a vacuum drying oven at 75 ℃ for 12 hours to obtain the extractant with high purity. Washing the prepared extractant with 0.1M hydrochloric acid for several times or crystallizing normal hexane to obtain the extractant with higher purity.
The extractant (designated as extractant E1) prepared by the above method had a purity of 99.9%.
FIG. 1 shows a process flow chart of the extractant prepared in the above way applied to the extraction and separation process of gold and other noble metals, and is shown in FIG. 1;
A1) weighing the extractant E1(0.18g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, and preparing a reverse extraction phase with gold, platinum, palladium, rhodium and copper concentrations of 10ppm and 0.2M hydrochloric acid aqueous solution and thiourea (reverse extractant) concentration of 0.1mM by using metal chloride or standard solution;
B1) respectively adding 5m L of the organic phase and the aqueous phase into a container, fully mixing the organic phase and the aqueous phase by means of oscillation (the oscillation time is 30 minutes, and the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, and extracting the organic phase;
C1) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (replacing the organic phase in the step A1) for repeated utilization rate determination), and finally obtaining the aqueous solution containing high-purity gold.
The results show that: the content of gold in the organic phase obtained in the step B1) is not less than 9.2ppm, the extraction rate is not less than 92%, the content of other metals is not more than 15ppm (the sum of the contents of the other metals), and the extraction rate of the other metals is not more than 37.5% (the total of the other metals); the gold content of the aqueous solution of the stripping phase (namely the aqueous solution containing high-purity gold) is not less than 9.0ppm, the stripping rate is not less than 97.8%, the content of other metals is not more than 1.5ppm, and the stripping rate of other metals is not more than 10%.
Determination of the recycling rate: in the experiment repeated 5 times, the extraction rate of the gold is not less than 90%, and the back-extraction rate is not less than 92%; the extraction rate of other metals is not more than 10 percent, and the back extraction rate is not more than 10 percent.
Example 2
1.52g (13.1mmol) of diglycolic anhydride and 2.87(11.9 mm) are weighed outol)R1R2NH(R1Selected from 2-ethylhexyl, R2Selected from 2-ethylhexyl) in a solvent of 20m L dichloromethane, reacting at 25 deg.C, clarifying the mixture gradually, and finishing the reaction (about 12h) when the mixture is completely clarified to obtain the extractant of formula (I) (wherein X is X)1And X2Is identically a-O-, R1And R2The same is 2-ethylhexyl); washing the prepared extractant with high-purity deionized water to remove impurities, adding magnesium sulfate into the product after washing, filtering to obtain a product without water, removing the organic solvent from the treated product through a rotary evaporation condenser, and drying in a vacuum drying oven at 75 ℃ for 12 hours to obtain the extractant with high purity. Washing the prepared extractant with 0.1M hydrochloric acid for several times or crystallizing normal hexane to obtain the extractant with higher purity.
The extractant (designated as extractant E2) prepared by the above method had a purity of 99.9%.
A1) Weighing the extractant E2(0.19g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, and preparing a reverse extraction phase with gold, platinum, palladium, rhodium and copper concentrations of 10ppm and 0.2M hydrochloric acid aqueous solution and thiourea (reverse extractant) concentration of 0.1mM by using metal chloride or standard solution;
B1) respectively adding 5m L of the organic phase and the aqueous phase into a container, fully mixing the organic phase and the aqueous phase by means of oscillation (the oscillation time is 30 minutes, and the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, and extracting the organic phase;
C1) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (replacing the organic phase in the step A1) for repeated utilization rate determination), and finally obtaining the aqueous solution containing high-purity gold.
The results show that: the content of gold in the organic phase obtained in the step B1) is not less than 9.6ppm, the extraction rate is not less than 96%, the content of other metals is not more than 16ppm (the sum of the contents of other metals), and the extraction rate of other metals is not more than 40% (the sum of other metals); the gold content of the aqueous solution of the stripping phase (namely the aqueous solution containing high-purity gold) is not less than 8ppm, the stripping rate is not less than 83%, the content of other metals is not more than 12.8ppm, and the stripping rate of other metals is not more than 80%.
Determination of the recycling rate: in the experiment repeated 5 times, the extraction rate of gold is not less than 90%, the back extraction rate is not less than 80%, the extraction rate of other metals is not more than 40%, and the back extraction rate is not more than 80%.
The results of examples 1-2 above show that: the novel extractant prepared in examples 1 and 2, which has high efficiency separation characteristics for noble metals, is used; in addition, the hydrophobicity of the extractant can be adjusted by the composition of the branched chain, wherein the branched chain of the extractant prepared in the example 1 is isooctyl, and the branched chain of the extractant prepared in the example 2 is 2-ethylhexyl; it can be seen that the extractant prepared in example 2 has good hydrophobicity, so that the extractant has improved recycling rate and is more environment-friendly.
Example 3
The separation among the noble metals of platinum, palladium and rhodium, and the separation of the noble metals of platinum, palladium, rhodium and other metal copper; wherein, when the noble metal contains gold, the extraction operation is performed from the following step a 1); when the noble metal does not contain gold, the extraction operation is performed from step a2) described below;
A1) weighing the extractant E1(0.18g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, and preparing a reverse extraction phase with gold, platinum, palladium, rhodium and copper concentrations of 10ppm and 0.2M hydrochloric acid aqueous solution and thiourea (reverse extractant) concentration of 0.1mM by using metal chloride or standard solution;
B1) adding 5m L of the organic phase and the aqueous phase into a container respectively, fully mixing the organic phase and the aqueous phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, extracting the organic phase, and using the residual aqueous phase in the step A2);
C1) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of oscillation (the oscillation time is 30 minutes, and the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (used for replacing the organic phase in the step A1) for determination of the recycling rate), and finally obtaining an aqueous solution containing high-purity gold;
A2) weighing the extractant E1(0.18g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, and preparing aqueous solution of platinum, palladium, rhodium and copper with concentration of 10ppm and hydrochloric acid concentration of 1.0M by metal chloride salt or standard solution, or preparing residual aqueous phase in the step B1) and stripping phase with thiourea (stripping agent) concentration of 0.1 mM;
B2) adding 5m L of the organic phase and the aqueous phase into a container respectively, fully mixing the organic phase and the aqueous phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, extracting the organic phase, and using the residual aqueous phase in the step A3);
C2) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of oscillation (the oscillation time is 30 minutes, the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (used for replacing the organic phase in the step A2) for determination of the recycling rate), and finally obtaining an aqueous solution containing high-purity platinum;
A3) weighing the extractant E1(0.18g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, and preparing aqueous solution of palladium, rhodium and copper with concentration of 10ppm and hydrochloric acid concentration of 0.2M or residual aqueous phase of the step B2) and reverse extraction phase with concentration of thiourea (reverse extractant) of 0.1mM by using metal chloride or standard solution;
B3) adding 5m L of the organic phase and the aqueous phase into a container respectively, fully mixing the organic phase and the aqueous phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, extracting the organic phase, and using the residual aqueous phase in the step A4);
C3) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of oscillation (the oscillation time is 30 minutes, and the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (used for replacing the organic phase in the step A3) for determination of the recycling rate), and finally obtaining an aqueous phase containing palladium;
A4) weighing the extractant E1(0.18g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, preparing aqueous solution of rhodium and copper with concentration of 10ppm and hydrochloric acid concentration of 0.2M or residual aqueous phase in the step B3) and reverse extraction phase with thiourea (reverse extractant) concentration of 0.1mM by using metal chloride or standard solution;
B4) respectively adding 5m L of the organic phase and the aqueous phase into a container, fully mixing the organic phase and the aqueous phase by means of oscillation (the oscillation time is 30 minutes, and the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, and extracting the organic phase to obtain an organic phase containing rhodium;
C4) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (replacing the organic phase in the step A4) for repeated utilization rate determination), and finally obtaining an aqueous phase containing rhodium.
From the above example 3, it can be seen that the extractant according to the invention can effectively achieve separation between noble metals and other metals, for example, separation between noble metals gold, platinum, palladium, rhodium.
Example 4
The extractant E1 prepared in example 1 was used, and the extraction and separation method was the same as that described in example 1 except that aqueous solutions of gold, platinum, palladium, rhodium and copper salts at concentrations of 10ppm and 0.2M, 0.5M, 1M, 2M, 4M, 5M, 7M and 10M, respectively, were prepared from metal chloride or standard solution. The results are shown in Table 1.
Table 1 extraction results of example 1 and example 4
Figure BDA0001237236300000151
The results of example 1 and example 4 above show that: since the concentrations of the aqueous hydrochloric acid solutions in the aqueous phases are different and the separation characteristics of gold from other metals and/or other noble metals are different, the extraction separation coefficient can be significantly improved by adjusting the concentrations of the aqueous hydrochloric acid solutions.
Example 5
The extractant E1 prepared in example 1 was used, and the extraction separation method differs from the extraction separation method described in example 1 only in that the extractant was dissolved in an organic solvent (kerosene) (50M L) to prepare a 0.01M extractant-containing organic phase.
The results show that: the content of gold in the organic phase obtained in the step B1) is not less than 9.7ppm, the extraction rate is not less than 97%, the content of other metals is not more than 17ppm (the sum of the contents of the other metals), the extraction rate of the other metals is not more than 42.5% (the total of the other metals), the content of gold in the aqueous solution of the stripping phase is not less than 9.5ppm, the stripping rate is not less than 97.9%, the content of the other metals is not more than 15.3ppm, and the stripping rate of the other metals is not more than 90%.
The results of example 1 and example 5 above show that: the organic solvents in the organic phase are different, the separation characteristics of gold and other metals and/or other noble metals are different, and the extraction separation coefficient can be obviously improved by selecting different organic solvents.
Example 6
The extractant E1 prepared in example 1 was used as the extractant, and the extraction separation method is the same as the extraction separation method described in example 1 except that 1) the shaking time of the extraction and the back extraction is 30 seconds, 90 seconds, 120 seconds, 150 seconds, 5 minutes, 15 minutes, 30 minutes, 45 minutes, 1 hour, 1.5 hours, 2 hours, 4 hours, 6 hours and 8 hours; 2) the resulting aqueous solution containing high purity gold was not back-extracted. The results are shown in Table 2.
Table 2 extraction results of example 1 and example 6
Figure BDA0001237236300000161
TABLE 2 (subsequent) extraction results of example 1 and example 6
Figure BDA0001237236300000171
The results of example 1 and example 6 above show that: the extraction and back extraction time is different, the separation characteristics of gold and other metals and/or other noble metals are different, the separability of the extractant can be enlarged by regulating and controlling the extraction time, and the extraction separation coefficient is improved.
Example 7
1.52g (13.1mmol) of thiodiglycolic anhydride and 2.87g (11.9mmol) of R are weighed out1R2NH(R1Selected from isooctyl, R2Selected from isooctyl) respectively dissolved in 20m L dichloromethane organic solvent, mixing the two solutions, reacting at 25 deg.C, clarifying the mixed solution gradually during the reaction, and reacting when the solution is completely clarifiedCompleting the reaction (about 12h) to obtain the extractant shown in the formula (I) (wherein X is1And X2Is identically a-S-, R1And R2The same is isooctyl); washing the prepared extractant with high-purity deionized water to remove impurities, adding magnesium sulfate into the product after washing, filtering to obtain a product without water, removing the organic solvent from the treated product through a rotary evaporation condenser, and drying in a vacuum drying oven at 75 ℃ for 12 hours to obtain the extractant with high purity. Washing the prepared extractant with 0.1M hydrochloric acid for several times or crystallizing normal hexane to obtain the extractant with higher purity.
The extractant (designated as extractant E3) prepared by the above method had a purity of 99.9%.
FIG. 1 shows a process flow chart of the extractant prepared in the above way applied to the extraction and separation process of gold and other noble metals, and is shown in FIG. 1;
A1) weighing the extractant E3(0.18g), dissolving in organic solvent (n-dodecane) (50M L) to obtain 0.01M organic phase containing the extractant, and preparing a reverse extraction phase with gold, platinum, palladium, rhodium and copper concentrations of 10ppm and 0.2M hydrochloric acid aqueous solution and thiourea (reverse extractant) concentration of 0.1mM by using metal chloride or standard solution;
B1) respectively adding 5m L of the organic phase and the aqueous phase into a container, fully mixing the organic phase and the aqueous phase by means of oscillation (the oscillation time is 30 minutes, and the oscillation temperature is 25 ℃), separating the two phases by means of centrifugation (or standing) of the fully mixed two phases, and extracting the organic phase;
C1) adding A3 m L organic phase and A3 m L stripping phase containing stripping agent into another container, fully mixing the organic phase and the stripping phase by means of shaking (the shaking time is 30 minutes, and the shaking temperature is 25 ℃), separating the two phases by means of centrifugation (or standing), extracting the organic phase (replacing the organic phase in the step A1) for repeated utilization rate determination), and finally obtaining the aqueous solution containing high-purity gold.
The results show that: the content of gold in the organic phase obtained in the step B1) is not less than 9.5ppm, the extraction rate is not less than 95%, the content of other metals is not more than 20ppm (the sum of the contents of other metals), and the extraction rate of other metals is not more than 50% (the sum of other metals); the gold content of the aqueous solution of the stripping phase (namely the aqueous solution containing high-purity gold) is not less than 9ppm, the stripping rate is not less than 94%, the content of other metals is not more than 3ppm, and the stripping rate of other metals is not more than 15%.
Comparative example 1
Dibutyl carbitol (DBC) is a commonly used extracting agent for extracting gold and other noble metals, 0.08g of extracting agent is weighed and dissolved in an organic solvent (n-dodecane) (50M L) to prepare a 0.01M organic phase containing the extracting agent, hydrochloric acid aqueous solution of gold, platinum, palladium, rhodium and copper with the concentrations of 10ppm and hydrochloric acid with the concentration of 1M and thiourea (stripping agent) with the concentration of 0.1mM can be prepared by metal chloride salt or a standard solution, 5M L of the organic phase and the aqueous phase are respectively added into a container, the organic phase and the aqueous phase are fully mixed by shaking (the shaking time is 12 hours and the shaking temperature is 25 ℃), the fully mixed two phases are separated by centrifugation (or standing), the organic phase is extracted, 3M L of the organic phase and 3M L of the stripping agent-containing the stripping agent are added into another container, the high-purity organic phase and the high-purity organic phase are separated by shaking (the shaking time is 12 hours and the fully mixed phase is 25 ℃) or standing).
The results show that: the gold content of the high-purity gold-containing aqueous solution is not less than 9ppm, the extraction rate is not less than 90%, the content of other metals is more than 16ppm (the sum of the contents of other metals), and the extraction rate of other metals is more than 40% (the sum of other metals); the gold content ratio of the aqueous solution of the stripping phase (namely the aqueous solution containing high-purity gold) is less than 8.5ppm, the stripping rate is less than 85%, the content of other metals is not more than 13.2ppm, and the stripping rate of other metals is more than 82%.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (13)

1. A noble metal extraction separation method is characterized in that an organic phase containing an extracting agent is adopted for extraction separation in the extraction separation method, and the structure of the extracting agent is shown as the formula (I):
Figure DEST_PATH_IMAGE002
formula (I)
Wherein, X1、X2Identical or different, independently of one another, from the group-O-or-S-; r1、R2Same or different, independently from each other selected from H, C1~30Linear or branched alkyl of (a); and R is1、R2Is not simultaneously selected from H;
the extraction separation method is suitable for extraction separation between gold and other metals and/or noble metals, between platinum, palladium and rhodium and other noble metals and/or other metals;
the method comprises the following steps:
judgment 1) first, it is confirmed whether gold is contained in the system to be separated, and if gold is contained, the procedure is started from step a1) below; starting from the following judgment 2) if gold is not contained;
A1) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11An aqueous phase P comprising an aqueous hydrochloric acid solution of gold and other metals and/or other noble metalsM11And an aqueous phase P containing a stripping agentB11；
B1) Will PE11And PM11Mixing, shaking and separating to obtain organic phase P containing goldE12And an aqueous phase P of hydrochloric acid containing other metals and/or other noble metals not containing goldM12；
C1) To PE12Adding PB11Mixing and shaking, separatingObtaining an aqueous phase P containing goldB12And an organic phase P 'containing an extractant'E11；
Judging 2) confirming whether platinum is contained in the system to be separated, and if platinum is contained, starting from the following step A2); if platinum is not contained, starting from the following judgment 3);
A2) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11An aqueous phase P containing platinum and an aqueous hydrochloric acid solution of another noble metal and/or another metal excluding gold and platinumM21Or directly using P separated in the step B1) aboveM12And an aqueous phase P containing a stripping agentB11；
B2) Will PE11And PM21Or PE11And PM12Mixing, shaking and separating to obtain an organic phase P containing platinumE22And an aqueous phase P containing an aqueous hydrochloric acid solution of a noble metal other than gold and platinum and/or of another metalM22；
C2) To P obtained in step B2)E22Adding PB11Mixing, shaking and separating to obtain water phase P containing platinumB22And an organic phase P' containing an extractant "E11；
Determining 3) whether palladium is contained in the system to be separated, and if palladium is contained, starting from step a3) below; if palladium is not contained, starting from the following judgment 4);
A3) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11An aqueous phase P comprising an aqueous hydrochloric acid solution of palladium and other noble metals and/or other metals, excluding gold, platinum and palladiumM31Or directly using P separated in the step B2) aboveM22And an aqueous phase P containing a stripping agentB11；
B3) Will PE11And PM31Or PE11And PM22Mixing, shaking and separating to obtain an organic phase P containing palladiumE32And an aqueous phase P containing an aqueous hydrochloric acid solution of a noble metal other than gold, platinum and palladium and/or of another metalM32；
C3) To step B3) to obtainTo PE32Adding PB11Mixing, shaking and separating to obtain water phase P containing palladiumB32And an organic phase P 'containing an extractant'E11；
Judging 4) confirming whether rhodium is contained in the system subjected to preliminary separation, and if rhodium is contained, starting from the following step A4); if the rhodium is not contained, ending;
A4) separately preparing an organic phase P containing an extractant for separating noble metals represented by the formula (I)E11Aqueous phase P comprising an aqueous hydrochloric acid solution of rhodium and of other noble metals and/or other metals not including gold, platinum, palladium and rhodiumM41Or directly using P separated in the step B3) aboveM32And an aqueous phase P containing a stripping agentB11；
B4) Will PE11And PM41Or PE11And PM32Mixing, vibrating and separating to obtain an organic phase P containing rhodiumE42；
C4) To P obtained in step B4)E42Adding PB11Mixing, shaking and separating to obtain water phase P containing rhodiumB42And an organic phase P '"containing an extractant'E11；
Wherein the organic solvent in the organic phase is n-dodecane or kerosene;
the hydrochloric acid aqueous solution containing gold and other metals and/or other noble metals is prepared by soaking gold and other metals and/or other noble metals in hydrochloric acid, the other metals are copper, and the other noble metals are platinum, palladium, rhodium, ruthenium, osmium, iridium and silver;
the hydrochloric acid aqueous solution containing platinum and other noble metals and/or other metals except gold and platinum is prepared by hydrochloric acid leaching of platinum and other metals except gold and platinum and/or other noble metals, wherein the other metals are copper, and the other noble metals are palladium, rhodium, ruthenium, osmium, iridium and silver;
the hydrochloric acid aqueous solution containing palladium and other noble metals and/or other metals excluding gold, platinum and palladium is prepared by pickling palladium and other metals and/or other noble metals excluding gold, platinum and palladium with hydrochloric acid, wherein the other metals are copper, and the other noble metals are rhodium, ruthenium, osmium, iridium and silver;
the hydrochloric acid aqueous solution containing rhodium and other noble metals and/or other metals except gold, platinum, palladium and rhodium is prepared by acid pickling rhodium and other metals and/or other noble metals except gold, platinum, palladium and rhodium, wherein the other metals are copper, and the other noble metals are ruthenium, osmium, iridium and silver;
the stripping agent is thiourea or hydrazine.
2. The extractive separation method according to claim 1, wherein the organic phase P containing the extractant for separating noble metal represented by the formula (I)E11The molar mass concentration of the metal is 0.005-4 mol/L, and the aqueous phase P of the hydrochloric acid aqueous solution containing gold and other metals and/or other noble metals isM11In the method, the concentrations of gold and other metals and/or other noble metals are 1-100 ppm respectively, and the concentration of hydrochloric acid is 0.005-10 mol/L;
the aqueous phase P containing platinum and an aqueous hydrochloric acid solution of another noble metal and/or another metal excluding gold and platinumM21Wherein the concentrations of platinum and other noble metals and/or other metals excluding gold and platinum are 1-100 ppm respectively, and the concentration of hydrochloric acid is 0.5-10 mol/L;
the aqueous phase P comprising palladium and an aqueous hydrochloric acid solution of another noble metal and/or another metal, excluding gold, platinum and palladiumM31Wherein the concentrations of palladium and other noble metals and/or other metals excluding gold, platinum and palladium are respectively 1-100 ppm, and the concentration of hydrochloric acid is 0.1-0.5 mol/L;
the aqueous phase P containing rhodium and an aqueous hydrochloric acid solution of other noble metals and/or other metals excluding gold, platinum, palladium and rhodiumM41Wherein the concentration of rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodium is 1-100 ppm respectively, and the concentration of hydrochloric acid is 0.005-0.1 mol/L;
the aqueous phase P containing the stripping agentB11Has a molar mass concentration of 0.01 × 10-3~1mol/L。
3. The extractive separation method according to claim 2, wherein the organic phase P containing the extractant for separating noble metal represented by the formula (I)E11The molar mass concentration of (a) is 0.01-2 mol/L;
the aqueous phase P of the aqueous hydrochloric acid solution containing gold and other metals and/or other noble metalsM11In the method, the concentrations of gold and other metals and/or other noble metals are respectively 5-30 ppm, and the concentration of hydrochloric acid is 0.005-10 mol/L;
the aqueous phase P containing platinum and an aqueous hydrochloric acid solution of another noble metal and/or another metal excluding gold and platinumM21In the method, the concentrations of platinum and other noble metals and/or other metals excluding gold and platinum are respectively 5-30 ppm, and the concentration of hydrochloric acid is 0.5-10 mol/L;
the aqueous phase P comprising palladium and an aqueous hydrochloric acid solution of another noble metal and/or another metal, excluding gold, platinum and palladiumM31Wherein the concentrations of palladium and other noble metals and/or other metals excluding gold, platinum and palladium are respectively 5-30 ppm, and the concentration of hydrochloric acid is 0.1-0.5 mol/L;
the aqueous phase P containing rhodium and an aqueous hydrochloric acid solution of other noble metals and/or other metals excluding gold, platinum, palladium and rhodiumM41Wherein the concentration of rhodium and other noble metals and/or other metals excluding gold, platinum, palladium and rhodium is 5-30 ppm respectively, and the concentration of hydrochloric acid is 0.005-0.1 mol/L;
the aqueous phase P containing the stripping agentB11Has a molar mass concentration of 0.05 × 10-3~0.5mol/L。
4. The extractive separation method according to claim 3, wherein the aqueous phase P containing the stripping agentB11Has a molar mass concentration of 0.1 × 10-3~0.1mol/L。
5. The extraction separation method according to any one of claims 1 to 4, wherein the oscillation time is 10 seconds to 20 hours; the extraction temperature is 10-50 ℃.
6. The extraction separation method according to any one of claims 1 to 4, wherein the volume ratio of the organic phase containing the noble metal separating extractant represented by the formula (I), the aqueous phase containing the aqueous hydrochloric acid solution of the metal, and the aqueous phase containing the stripping agent is (0.5-1.5): (0.5-5): 0.5-5).
7. The extraction separation method according to claim 6, wherein the volume ratio of the organic phase containing the extractant for noble metal separation represented by the formula (I), the aqueous phase containing the aqueous hydrochloric acid solution of the metal, and the aqueous phase containing the stripping agent is (0.5-1.5): 1.5-2.5.
8. The extractive separation method of any one of claims 1 to 4, wherein R is1、R2Same or different, independently from each other selected from H, C1~18Linear or branched alkyl of (a); and R is1、R2Not simultaneously selected from H.
9. The extractive separation process of claim 8, wherein R is1、R2Identical or different, independently of one another, from H, n-octyl, n-hexyl, isohexyl, n-butyl, 2-ethylhexyl, isobutyl or isooctyl; and R is1、R2Not simultaneously selected from H.
10. The extractive separation method according to any one of claims 1 to 4, wherein X is1、X2And the same is selected from-O-.
11. The extractive separation method according to claim 8, wherein X is1、X2And the same is selected from-O-.
12. The extractive separation method of claim 9, wherein X is1、X2And the same is selected from-O-.
13. The extractive separation method of any one of claims 1 to 4, wherein the extractant has a purity of 90% or more.
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